有机液体储氢载体催化脱氢技术研究进展  

Research Progress in the Catalytic Dehydrogenation Technology of Liquid Organic Hydrogen Carriers

作　　者：潘伦[1] 韩泽昊 闫晓 高睿杰 张香文[1] 邹吉军[1] Pan Lun;Han Zehao;Yan Xiao;Gao Ruijie;Zhang Xiangwen;Zou Jijun(School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China)

机构地区：[1]天津大学化工学院,天津300072

出　　处：《天津大学学报（自然科学与工程技术版）》2024年第6期557-574,共18页Journal of Tianjin University：Science and Technology

基　　金：国家自然科学基金资助项目(22222808,21978200)。

摘　　要：绿氢(可再生能源制氢)的开发及利用是推动能源绿色转型和实现“双碳”目标的重点发展方向之一.然而,大规模绿氢的安全储运技术仍需进一步完善.以环烷烃/芳烃为主的有机液体储氢载体(LOHCs)体系因其高储氢密度、安全高效、运输方便等优势成为绿氢长距离大规模输送的关键技术.相比于工艺成熟的芳烃加氢技术,富氢LOHCs(环烷烃)脱氢技术开发的难度较大,是近年来研究的热点.本文系统综述了环己烷(CH)、甲基环己烷(MCH)、十氢萘(DHN)和全氢二苄基甲苯(H18-DBT)4类典型富氢LOHCs脱氢技术的研究进展.基于目前的研究结果,阐述了单环烷烃(CH、MCH)和多环烷烃(DHN、H18-DBT)的脱氢反应路径和机理,重点从活性组分和载体两方面总结了脱氢催化剂的设计思路、构效关系和研究进展,详细分析了基于不同模型的富氢LOHCs脱氢动力学,探讨了4类典型脱氢反应装置的优缺点.总体来讲,环烷烃作为LOHCs距离工业化应用还有一段距离,继续完善环烷烃脱氢动力学和脱氢机理、提高Pt系催化剂的催化活性和稳定性、开发具有实际应用意义的非贵金属催化剂以及优化反应器结构成为未来环烷烃脱氢技术研究需要聚焦的难点.Hydrogen produced using renewable energy,i.e.,green hydrogen,can achieve zero carbon emission and is one of the ways to promote green energy transition and realize carbon neutrality.Hydrogen storage and transportation technology imposes great difficulties on the large-scale application of green hydrogen.Liquid organic hydrogen carriers(LOHCs),which mainly include cycloalkanes/aromatics,have become a key technology for longdistance hydrogen delivery because of their high hydrogen storage density,safety and efficiency,and convenient transportation.Compared with the mature aromatic hydrogenation technology,the development of hydrogen-rich LOHC(cycloalkanes)dehydrogenation technology is more difficult and has been a hot research topic in recent years.This paper systematically reviews the research progress in the dehydrogenation technologies of four typical types of cycloalkanes:cyclohexane(CH),methylcyclohexane(MCH),decahydronaphthalene(DHN),and fully hydrogenated dibenzyltoluene(H18-DBT).Herein,the dehydrogenation reaction pathways and mechanisms of monocyclic(CH and MCH)and polycyclic alkanes(DHN and H18-DBT)are described based on the current research results.Furthermore,this paper summarizes the design ideas,structure-performance relations,and research progress in dehydrogenation catalysts with a focus on active components and carriers,analyzes the dehydrogenation kinetics of hydrogen-rich LOHCs in detail based on different models,and discusses the advantages and disadvantages of four types of typical dehydrogenation reaction devices.In general,the industrial application of cycloalkanes as LOHCs remains a long way off.Continuous improvements in the dehydrogenation kinetics and dehydrogenation mechanisms,enhancements in the catalytic activity and stability of Pt catalysts,development of nonprecious metal catalysts with practical applications,and optimization of the reactor structure have become the key points of the future research on cycloalkanes dehydrogenation technology.

关 键 词：有机液体储氢载体 环烷烃 催化脱氢 脱氢催化剂 反应动力学 

分 类 号：TQ116.2[化学工程—无机化工]